Process for breaking petroleum emulsions



Patented Aug. 15, 195 0 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a corporation of Delaware No Drawing." Application May'31, 1947,

Serial No. 751,600

a a 1 This invention relates to processes or procedures particularly adapted for preventing, breaking, or resolving emulsions of the water-inoil type and particularly petroleum emulsions.

' Complementary to the present invention is our companion invention concerned with the new chemical products or compounds used as the demulsifying agent in the present processes or procedures, as well as the application of such products in various other arts and industries, along with methods for manufacturing said new chemical reagents which are of outstanding value as demulsifiers. See our co-pending application, Serial No. 751,625, filed May 31, 1947 (now Patent No. 2,499,360,-dated Mar. 7, 1950) Another object of our present invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil-type that are commonly referred to as cut oil, roily oil,

emulsified oil, etc., and which comprise finedroplets of naturally-occurring Waters or brines dispersed in a more or less permanent state throughout the oil which .constitutes the continuous phase of the emulsion.

And still another object of our invention to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil, and relatively soft waters or brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

Demulsification as referred to in the present application includes the preventive step of commingling'the demulsifier with the aqueous component which might, in absence of such demulsiiler, have become ne phase of anoil and water emulsion. It also includes mixing the demulsioxyalkylated derivatives; are valuable as demulsi- ,fl r as a des ribed.

21 Claims. (Cl. 252--340) To be usable in the present invention, a product must have the required composition and must be surface-active and hydrophile, i. e., it must be water-soluble, water-dispersible, or selfemusifiable. Products of the kind disclosed herein are themselves useful in various arts. In addition, they are useful as intermediates in the preparation of other products, as will be mentioned below.

To make the products used in our present process requires first the preparation of diphenylolmethanes from certain aldehydes and phenols, in the proportions and under the conditions set out in detail below; and the subsequent oxyalkylation of such parent compounds by the use of certain oxyalkylating agents to produce a principal embodiment of our reagent. Such oxyalkylated products may themselves be used in the present process. They may also be used as intermediates in preparing a second principal embodiment of our reagent. They are also useful as intermediates in the preparation of certain derivatives not included within either the present invention or the invention covered by our above-recited co-pending application.

The reagents of this invention may be visualized as substituted methanes, in which two of the four methane carbon valences are satisfied by phenolic residues of specified composition; one of the two remaining positions is occupied by hydrogen; and the last position is occupied either by hydrogen or by a hydrocarbon radical, whether of the alkyl, aryl, aralkyl, acyclic, cyclic, or alicyclic type, depending on the nature of the aldehydic reactant used. The reagents may likewise be easily visualized as consisting of two modified phenolic residues connected by a methylene or a mono-substituted methylene bridge.

In 0ur reagents, the molecule contains two residues derived from certain di-functional or tri-functional monocyclic and monohydric phenols or a mixture thereof; but they are usually derived from (ii-functional phenols. Di-functional (xii-reactive) phenols, to be suitable as reactants here, must contain one hydrocarbon substituent in the para position. Such hydrocarbon substituent may contain from 1 to more than 9 carbon atoms, e. g., it may contain as many as 24 carbon-atoms. We prefer that it contain at least 6 to 8 carbon atoms. In the case of the tri-functional phenolic reactants, only those having hydrocarbon substituents containing 9 carbon atoms or more, and occupying the 3,5 position, aresuitable. In the case of such tri-funcvtional phenolic reactants, there is no substituent group or radical to be considered, as to the 2,4,6 position, it being occupied by hydrogen.

Mono-functional (mono-reactive) phenols are not included as usable reactants to produce our reagents. See our co-pending application, Serial No. 586,269, filed April 2, 1945, (now Patent No. 2,430,003, dated Nov. 4, 1947) in this connection.

The aldehydic reactant is present for the purpose of supplying the connecting bridge or link between two molecules of the phenol. The proportion of aldehydic reactants is carefully controlled, So as to produce a maximum amount of diphenylolmethane. We have found that if one uses 1 mol of aldehyde for 2 mole of phenol, i. e., the theoretical proportions of reactants, the re-- action is inclined to be somewhat short of com plete. We have therefore found it advisable to use slightly larger than theoretical proportions of aldehydic reactant, e. g., 1.05 or possibly as much as 1.10 mols of aldehyde for 2 mols of phenol. An appreciably larger proportion of the aldehydic reactant should not be employed be-- cause it is conducive to the formation of molecules containing more than 2 phenolic nuclei each and these are distinctly not included within the scope of our invention. It appears, how ever, that some slight excess of aldehyde, of the order stated, is desirable. If a minor proportion of some product containing 3 phenolic nuclei in the molecule happened to be formed in the preparation of our reagent, its presence would not be detrimental to such products use in the applications stated below. Such impure or, rather, technically pure product is still to be considered as coming within our invention. The same is true if any uncombined excess of phenol happens to be present.

.Use of an appreciably smaller ratio of aldehyde to phenol than 1 to 2 merely results in incomplete combination of the phenol, the amount remaining uncombined contributing little or nothing to the value Of the product and at the same time raising its cost. Therefore, reactant proportions should be quite closely adhered to, and should be of the order of those just recited above.

While we include a sharply limited class of trifunctional phenols within the reactants usable to produce our reagents, we greatly prefer to employ the particular class of di-functional phenols noted herein.

'Para di-functional phenols are sometimes prepared from raw materials which contain methyl groups in either or both positions 3 and 5 (the meta position). Since such 3,5 position is not affected by reactions of the kind just discussed above, we specifically include di-functional phenols prepared from meta-cresol or 3,5 xylenol (i. e., (ii-functional phenols in which either or both the 3 and the 5 positions are occupied by methyl groups) within the class of raw materials for producing our reagents.

Mixtures of di-functional phenols may be'employed to produce our reagents, instead of a single member of the specified class. But not all difunctional phenols are usable. These same statements apply to -tri-functional phenols.

To be acceptable for use herein, a (ll-functional phenol must contain a substituent in the para position, which substituent is a hydrocarbon radical. Such hydrocarbon radical may contain from 1 to more than 9 carbon atoms. Forexample, it may contain 24 carbon atoms, without departing from our invention. We have already stated that we prefer to employ di-functional phenols whose substituent radicals contain at least 6 to 8 carbon atoms. The hydrocarbon radicals may be alkyl, aryl, aralkyl, acyclic, cyclic, or alicyclic. It is sometimes desirable to produce our reagent from a phenol containing an aryl substituent, and subsequently to convert such aryl substituent to a cyclic radical by conventional hydrogenation procedure, e. g. so it may be used where aromatic derivatives are potentially hazardous, as in cosmetics. Any such hydrogenation procedure must of course not destroy necessary functional groups in our products, or the intermediates used to produce them, like the phenolic hydroxyl groups or the alcoholic hydroxyl groups introduced by oxyalkylation, as described below.

The phenols used as reactants to prepare our reagents are specified to be monocyclic phenols, in the sense that they do not contain a condensed or fused ring. The naphthols are specifically excluded from the present application. Our

phenolic reactants may, however, have cyclic substituents, as in p-phenylphenol, or may contain an aromatic ring as part of an aralkyl substituent, etc. They are also required to be monohydric, i. e. they contain only one phenolic hydroxyl group per molecule.

In our products, both phenolic hydroxyl groups present in the parent diphenylolmethane, as prepared from a di-functional or tri-functional phenol and an aldehyde, have been replaced by a residue obtained from an alpha beta low molal alkylene oxide. The alkylene oxides whch we may use in preparing our reagents are limited to those containing 4 carbon atoms or less. They consist of ethylene oxide, propylene Oxide, butylene oxide, glycide, and methylglycide. Glycide may be considered to be hydroxypropylene oxide; and methylglycide, hydroxybutylene oxide.

Such alkylene oxides react with various substances, including phenols, to introduce one or more divalent alkyleneoxy groups, i. e., ethylene- 0xy--C'2H4O; propyleneoxy, -C3HeO'; butyleneoxy, -C4HsO-, or gene ally, --CnH21LO'-; or, in, the case of glycide and methylglycide, hydroxypropyleneoxy (C3Hs(OI-I)O-) or hydroxybutyleneoxy (-C4I-I1(O H) O-.), into the phenol molecule. Such alkylene oxide residue is interposed between the phenolic hydroxyl groups oxygen atom and its hydrogen atom. The result of this reaction is to convert the phenolic hydroxyl group into a glycol or hydroxylated glycol radical, one alcoholic hydroxyl group of which has been etherified with the phenolic residue, and the other or others. are free to particpate in any subsequent desired reactions. Depending on the proportion of alkylene oxide available and the conditions under which reaction is conducted, it is possible to introduce from 1 to as many a 60 or more alkyleneoxy units at each phenolic hydroxyl group, in this manner. In the present invention, we desire to specify that from 1 to 60 such units may be present for each original phenolic hydroxyl group in our reagents, so long as they retain certainspecified properties stated in detail below.

Because glycide and methylglycide are so infrequently employed, we shall confine our subsequent remarks below essentially to ethylene oxide, propylene oxide, and butylene oxide. It must be always remembered that when we speak henceforth of alkylene oxide residues, or illustrate our statements by references to one or more of the three non-hydroxylated members of our class,

we nonetheless always include glyc ide and methylglycide as full equivalents thereof. when we refer to glycol or polyglycol radicals herein, it is to be understood that hydroxyglycol or hydroxypolyglycol radicals are meant if the reactant is glycide or methylglycide. Glycide is so unstable that its use is not recommended, because of the hazard involved. It nevertheless comes within the purview of our invention. Mixtures of all our alkylene oxide reactants may be used, if desired, instead of any single one of them.

In our simpler products, then, the two phenolic hydroxylic groups of a diphenylolmethane have been converted into two glycol or polyglycol radicals having one free alcoholic hydroxyl group (in the case of glycideand methylglycidederived reagents, two or more) each. In our more complex reagents, such free alcoholic groups have been esterified, e. g., with a higher fatty acid, to

produce fractional or total esters. Detailed consideration of this phase of our invention is deferred momentarily.

The radical or residue which appears in our reagents as a bridge or link between the two modified phenolic radicals discussed above is obtained from a suitable reactive aldehyde containing not more than 8 carbon atoms. Such aldehyde may be aliphatic; it may be aromatic; or it may be cyclic. The simplest aldehydic reactant is formaldehyde; and because of its wide availability, low cost, and high reactivity in the present invention, we name it as our generally preferred reactant of this class. Its cyclic polymer, trioxane, may sometimes be employed to advantage. Its homologs, such as acetaldehyde or its polymer paraldehyde, propionaldehyde, butyraldehyde, and heptaldehyde, are obvious equivalents. Aromatic aldehydes like benzaldehyde are usable. Furfuraldehyde, representative of the class of heterocyclic aldehydes, is usable, etc. Obviously, where a material, although an aldehyde, possesses some more reactive functionality than its aldehydic character, it may not react as an aldehyde here, and hence may be unsuitable for use in preparing our reagents. Mixtures of suitable aldehydes containing less than 9 carbon atoms are usable to prepare our reagents.

i To summarize the foregoing briefly, our reagents are prepared from diphenylolmethanes which have themselves been obtained from low molal aldehydes and certain di-functional or trifunctional phenols, but not from mono-functional phenols. If procurable commercially, such diphenylolmethanes may be purchased rather than prepared. Such diphenylolmethanes are then subjected to oxyalkylation by means of a low molal oxyalkylating agent, in which process from 1 to 60 alkyleneoxy residues are introduced at each phenolic hydroxyl group, between the oxygen and hydrogen atoms thereof. Such oxyalkylated diphenylolmethanes are themselves an important embodiment of our inventions reagents. Their fractional or total esters, particularly those of high molal monocarboxylic acids, constitute a second important embodiment of our reagents.

, Our reagents may be illustrated by the following type formulas:

Rr-(B-R I R: imoRonom-rs-mo (R4O)n 7 In the first formula, R1 refers to a radical derived from a di-functional phenol in which the hydrocarbon substituent in the para position may possess from 1 to 24 carbon atoms, or derived from a tri-functional phenol having a 3,5 hydrocarbon substituent possessing at least 9 carbon atoms, and not more than 24 carbon atoms. The two R1 radicals may be the same or they may be different. Each R1 no longer possesses its original phenolic hydroxyl group, the latter having been replaced by residues obtained from alkylene oxide reactants and which possess terminal alcoholic hydroxyl groups, in free or esterified form.

In other words, the radicals R1 may be further detailed as in the second formula shown, where they are seen to consist of the radical wherein R3 is the phenolic nucleus containing a substituent hydrocarbon radical as above defined; R4 is an alkylene or hydroxyalkylene radical, either -C2H4*, -C3He-, C4Ha, C3H5(OH) or C4H1(OH) n is a number between 1 and and R7 is either hydrogen or the acyl radical of a high molal or a low molal monocarboxylic acid, with the limitation that at least one of the two occurrences of R7 must represent the acyl radical of a high molal monocarboxylic acid if either is acyl, as explained further below. R2 in both formulas may be either hydrogen or an organic radical; but at least one occurrence must represent hydrogen. (Where both occurrences of R2 represent hydrogen, formaldehyde was the parent aldehydic reactant. Where benzaldehyde was the aldehyde employed, the second R2 would represent the CeHs radical. If furfuraldehyde were the aldehyde used, the second occurrence of R2 would represent the cyclic radical, Cal-I30. If acetaldehyde were used, the second R2 would represent the aliphatic radical, CH3. These examples are illustrative.)

To detail this last generic formula still further, so as to show the phenolic residue in clearer fashion, the following formula is offered:

R2 R7(O R4 n0 R5R5---R R5O (R40) "R1 t. In this formula, one occurrence of R2 represents hydrogen" and the other occurrence represents either hydrogen or an organic radical containing '7 carbon atoms or less. R4 is an alkylene radical containing from 2 to 4 carbon atoms (and also containing a hydroxyl group if derived from glycide or methylglycide) The n occurrences of the alkyleneoxy radical R40 number between 1 and 60, for each occurrence of n shown. R5 is a hydrocarbon radical containing from 1 to 24 carbon atoms if located in the para position of a parent di-functional phenol, or else containing 9 carbon atoms to 24 carbon atoms if located in the 3,5 position of a parent tri-functional phenol. Re is a monocyclic aromatic ring, which may contain a methyl group in either or both the 3 and 5 positions, if the phenol was di-functional. R7 represents hydrogen or an acyl radical derived from a monobasic carboxylic acid having 1 to 32 carbon atoms, at least one occurrence of R7 in every case being the acyl radical of a monocar- 7. boxylic acid having 8 to 32 carbon atoms, if either is acyl. 7

Of the reagents included within the scope of this invention, we prefer most of all to employ those in which at least one, and preferably both, molecules of the (ii-functional phenol employed have substituent groups which are hydrocarbon radicals containing at least 6 or even 8 carbon atoms. In the case of tri-functional phenols, of course, we have specified a minimum of 9 carbon atoms in the hydrocarbon substituent radicals of such reactants.

The level of oxyalkylation employed to produce satisfactory reagents Will depend upon a number of factors. In all cases, however, the ultimate product must possess surface-activity and must be hydrophile, to come within our inven tion. Since ethylene oxide possesses the greatest oxygen-to-carbon ratio of the non-hydroxylated alkylene oxides which are usable, it will ordinar ily require fewer mols of it to produce a required level of surface-activity than it would of butylene oxide, for example. For some purposes, how ever, it may be desirable to employ butylen'e oX= ide rather than ethylene oxide, in spite of the above fact. Sometimes an intermediate product may have a somewhat unsatisfactory surfaceactivity; but this is immaterial so long as the ultimate product, asserted to come within our invention, has the required surface-activity.

For some purposes, such as demulsification of petroleum Water-in-oil emulsions, the preferred reagent usually has a relatively high degree of water-solubility. For other uses, lower levels thereof, probably more properly to be termed Water-dispersibility or self-emulsifiability, may be preferable. All our reagents are hydrophile, however; and, as such, all possess either watersolubility, water-dispersibility, or self-emulsifiability in water.

The, reagents exhibit great versatility and utiL- ity as one goes from minimum to maximum hydrophile characteristics in them by varying the proportion of alkylene oxide employed in their preparation. Minimum hydrophile properties may appear, for instance, when about two ethyleneoxy radicals have been introduced for each phenolic hydroxyl group originally present, Such minimum hydrophile property means that the product shows at least self-dispersibility or self-emulsiiiability in distilled water at from 30 to 60 (3., in concentrations between 0.5% and Such minimum dispersibility tests are preferably conducted in absence of water-insoluble so1vont's. Such sol or dispersion should be at least semi-stable, i. e., it should persist for from 30 minutes to 2 hours without showing aiififeciable separation. Of course, water-insoluble solvents may be present; and if the mixture of reagent and such insoluble solvents is at least semi stable, then obviously the solvent-free reagent would he even more watendispor'sibie.

The product may be so slowly dispersible, e. g], because of solid or semi-solid character, that it is difficult to re are su'ch dispersioil. In such cases", mixing the product with approximately an equal proportion or less of an alcohol lik'e meth- 1 or ethyl alcohol, or with ethylene glycol di= ethylether or diethylene glycol ciethylether, etc, win result in the formation of a readily dispersi= his material. The amount of solvent so included in the final aqueous dispersion is insignificant,

since the latter is 0.5% to 5% concentrated to oiiyalkyl'ated diphenyioimothahe. t

More visual examination of mixtures of the reagent with waterhiay sumce to indicate surfaceactivity, i. e.-, the product produces a homogene= ous' mixture which foams or shows emulsifying power. All these properties are related through adsorption at the interface, for example, at the gas liquid or the liquid-liquid interface. If d'e= sired, surface-activity may be measured in any of the quantitative methods for determining sur= face and interfacial tension, such as by means of a DuNouy tensiometer or a dropping pipette;

From the standpoint of surface=activity, it will be apparent that the present reagents represent a class of materials differing from each other by small increments, as the oxyalkylating agent and proportions of oxyalkylating agent are "varied' Employing different homologous phenolic react ants and different homologous aldehydic react ants, one is enabled to produce with ni'cety a product of any desired surface-activity charac= teris'tics.

As stated above, among the principal eiribodl mehts of our reagents are certain esterifid ae= rivatives of the foregoin oxyalkylateol dipheiiyl olmethanes, which themselves constitute another important embodiment thereof. Since the alkylated diphenylclrhethanes possess at least two alcoholic hydrexyl roups, they are capable of reacting With one fnol or an aeidic reactant t6 produce a fractional ester; or with two or more mols of such acidic reactant to produce total esters. Both ester forms are included within the present invention, 50 long as the acidic reach ants employed meet the following specifications. (For simplicity, we are proceeding he eina'fte'r as if the oxyaikyiatce' ciphenyiomet ane were de= rived from a hofi-hydroxylated alkylene oxide.

and therefore as if such product ossessed only two alcoholic hydroxyl groups. We have already specified that glycine and hiethpsiycide the suit able ox alhyiatihg agents to produce our re agents. We re eat that statement to make it plain that in some instances our simple oxyaikyiated diphei'iyioiinethane products ma contain four or more rather than two aicohoiichy= oroxyi grou s.)

The acidic reactant employed to produce such fractional or tots-i ester ma be any moiiobasic carbcxyii'c acid, whether saturated or not, which has 8 carbon atoms and not more than 32; lin chided among such acceptable acidic reactants are the higher fatty acids, petroleum acids like the naphthenio acids and acids produced by the oxidatidn'of petroleum rosin acids like ate etic-acic, etc. or all the acce table acids of this general class, we prefer to employ the higher fatty acids containing from 8 to '32 carbon atoms. we have foun the mod fied higher fatt a ids equivalent to the fatty acids themselves. For example, the chlorinated, bromine-ted, nyurogom ated modifications may b substituted for the sim le acids. other modifications are suitable, so long as they' retain the fundamental Chlffifif teristics of the fatty acids, e. are capable of formin alkali salts which are soap-like or detergentdi e in character. instead or the acids, the acyi chlorides or acid anhydi'ides may be em= ployed in the estefificationreaction, just as may any other functional equivalents of the free acids. For example, iow iiiciai esters of such acids, like the methyl or ethyl esters, may be i1ti= lizecl to advantage in some instances. They are eifective by virtue of an alcoholysis reaction in which the alkyl group is displaced from the ester by the diphenylolmethane residue, with concomitant liberation of methyl or ethyl alcohol. The

use of such low molal esters is attractive in that any excess thereof, and also the methyl and ethyl alcohol produced in such alcoholysis reaction, may be readily removed from the reaction mass by distillation.

If desired, mixed esters of our diphenylolmethanes may be prepared by using different high molal monocarboxylic acids in the foregoing esterification step. Furthermore, so long as a high molal monocarboxylic acid is employed to esterify at least one of the alcoholic hydroxyl groups of the diphenylolmethane, monocarboxylic acids having fewer than 8 carbon atoms may be employed to esterify the remaining alcoholic hydroxyl group or groups. Acids such as acetic, hydroxyacetic, lactic,'butyric, propionic; heptoic, etc., are useful, as are their chlorides, anhydrides, and other obvious equivalents capable of supplying the acyl radical required in the esterification.

Of the ester forms of our reagents, we prefer those prepared from higher fatty acids having 18 carbon atoms, and particularly such higher acids as are unsaturated. Among such fatty acids are oleic, linoleic, linolenic, and ricinoleic acids. If desired, the mixed fatty acids recovered from the splitting of any selected saponifiable fat or oil, such as cottonseed oil, soybean oil, corn oil, etc. may be employed as the esterifying agent.

All such high molal monocarboxylic acids above recited are members of the class of detergentforming acids, because their alkali salts are soaps or soap-like products. Esters of unsaturated C-ls acids with our oxyalkylated diphenylolmethanes are particularly desirable where our reagents are to be used as demulsifiers for resolving petroleum emulsions of the water-in-oil type.

The ester forms of our reagents are useful as intermediates in further reactions, so long as they retain a functional group capable of participating in such reaction. For example, the fractional esters still contain one acoholic hydroxyl group per molecule, which is susceptible to further esterification. The total esters are likewise often useful in further reactions. For example, conjugated double bonds in the fatty acid residue are reactive, the alcoholic hydroxyl group of the ricinoleic acid residue is reactive, etc.

Having described the reagents of our invention in broad outline, we propose now to consider certain aspects thereof in greater detail.

Our reagents may be prepared in any desired manner; but ordinarily they are prepared in two or three steps. First, the diphenylolmethane is prepared; then it is oxyalkylated; and finally derivatives of such oxyalkylated products, such as the esters, are prepared from them. Manufacture of the parent diphenylolmethane wil be first considered. It usually involves formaldehyde and a phenolic reactant of the kind described in detail above. Condensation reactions of this type are well known and do not require detailed description. We might note that if furfuraldehyde is used as the aldehydic reactant, alkaline condensing agents or catalysts may preferably be employed; otherwise acidic catalysts are usually preferred. The condensation reactions produce diphenylolmethanes which are oily to very viscous semi-solids, or even solids, in appearance.

In all cases, substantially 2 mols of phenol are combined with 1 mol of aldehydic reactant. The reactant proportions are usually preferably slightly in excess of 1 mol of aldehyde to 2 mols of phenol, in order to facilitate completion of the reaction, as mentioned above. For example, such ratio may be 1.05 to 2 or 1.1 to 2, or possibly as great as 1.2 to 2, without departing from our invention. Increasing the aldehyde proportion unduly is to be avoided, because it tends to give products containing more than 2 phenolic nuclei in the molecule. Increasing the phenol proportion, i. e., reducing the aldehyde proportion unduly, may result in waste of phenol in that it will remain uncombined with the aldehyde. Such excess is therefore to be avoided. (It will probably become oxyalkylated, however.)

Note that, for our purpose, the resulting diphenylolmethane need be only technically pure. In other words, if it contains even as little as 65 or 70% of the desired diphenylolmethane, the product is frequently acceptable. The remainder, a composition not included within our invention, is usually inert rather than positively harmful. Of course, it may needlessly increase the cost of the product to have less effective or ineffective by-products or uncombined materials present. We naturally prefer to have the highest quality product obtainable. Excess free phenol, if volatile, may be recovered by distillation and empoyed to make later lots of the product, if desired.

Since the phenolic reactant is water-insoluble and frequently solid, and the preferred aldehydic reactant, formaldehyde, is usually employed as the commercial aqueous solution of 37-40% concentration, we have found it most desirable to employ, in addition to heat and vigorous agitation, a minor proportion of a wetting or emulsifying agent to promote emulsification of the mixture. See U. S. Patent No. 2,330,217, dated September 28, 1943, to Hunn, for examples of such preferred procedure as applied to the manufacture of resins. The following examples illustrate convenient procedures for preparing the diphenylolmethanes containing two phenolic nuclei, which are the parent substances of our reagents. While our products are distinctly not resins, because the latter have different properties and commonly contain 3 or more, and usually 4 or 5 or more phenolic residues, the Hunn procedure noted is applicable here.

DIPHEN'YLOLMETHANE Example 1 Mix 244 lbs. of 1,3,4, xylenol (2 mols) with 85 lbs. of 37% formaldehyde (1.05 mols), 4 lbs. of concentrated hydrochloric acid, and 1.5 lbs. of Nacconal NRSF (a product of National Aniline Co.) in a vessel equipped with reflux condenser, stirrer, thermometer, and cooling coils. This material, as is well known. is a monoalkyl (Cm-C20, principally Cir-C14) benzene monosulfonic acid sodium salt. Heat to 0., where a mild exothermic reaction sets in, raising the temperature to 100-105 C. A thin creaminessis noted after 15-30 minutes of refluxing. Reflux for 1 hour; add 100 lbs. of xylene as a solvent for subsequent oxyalkylation and also to facilitate removal of water from the reaction mass. Distill the water of solution and of reaction, with the xylene, using a trap arrangement which permits return of the xylene to the vessel, but removal of water as distilled. The resulting product, when solvent-free, is soft, tacky, xylene-soluble, and a clear amber in color. Molecular weight determination indicates about -90% of our desired reagent is present in the product. The purity may be increased to about or more by vacuum distillation.

1 i DIPI-IEN'YLOLMETHANEL Example. 2.-

Procedure is the same as in the foregoing example, except that p-phenylphenol is substitiltedv for 1,3,4 xylenol. The resulting product, when. solvent-free, has physical characteristics quite similar to those of the. foregoing product.

DIPHENYLOLMETHANE Example 3 Proceed similarly to Example 3 above, except substitute p-phenyIpheno-l' for p-cyclohexylpheno], in molecular proportions. The large amount of solvent was employed as in the preceding eX- ample, and for the same reason. The resulting product, when solvent-free, is dark amber in color, soft and tacky, slightly opaque, and sufiiciently xylene-dispersible to permit of subsequent oxyalkylation.

DIPHENYLQLMETHANE Example 5 Use. p-ethylphenol, 244, lbs; butyraldehyde, 75.6 lbs. (molal ratio, 2 to 1.05); concentrated sulfuric acid, 4112s.; and. Xylene, 1.001bs. Add. the p-ethylphenol and the concentrated sulfuric. acid to a vessel equipped as in Example 1,, above. Raise the temperature tov 150 C. Introduce the aldehyde slowly, the temperature gradually receding as water is formed, to 100-110 C. Reflux the mass for 1 hour, add the 100 lbs. of xylene, and then distill the water to a temperature of 150 C. This is essentially the procedure employed in U. S. Patent No. 2,373,058, dated April 3, 1945, to Silberkraus. The product, when solvent-free, is very-soft-to-fiuid, dark red, clear, and xylene-soluble.

DIPHENYLOLMETHANE.

Use p-ethylphenol, 244 lbs.; heptaldehyde,11,9.5 lbs. (molal ratio. 2 to 1.0.5,). concentrated, sulfuric acid, 4 lbs. and xylene, lbs. Proceed as in Example 5v above. The product, when solvent-free, is very-soft-to-fluid, xylene-soluble, clear, and dark red incolor.

DIPHE'NYLOLMETHANE Example 7 Use 1,3,4 xylenol, 244. lbs.; heptaldehyde, 119.5 lbs. (molal ratio, 2 to 1.0.5); concentrated sulfuric acid. 4 lbs; and xylene, 100 lbs. Proceed as. in Example 5 above. Heating is stopped at C the exothermic reaction carrying the temperature to C. as the aldehyde is. added, before b inni g to drop with formation of water of reaction. The water is distilled as before; The product, when solvent-free, is very-soft-to-fiuid, reddish-black in color, clear, and xylene-soluble.

I2 5 DIPHE'NYLOLMETHANE- Example 8.

Use p-cyclohexylphenol, 352; lbs; butyraldehyde, 75.6 lbs. (molal ratio, 2 to 1.05); concentrated sulfuric. acid,'4 lbs.; and xylene, 100 lbs. Proceed as in Example 5 above, except add the xylene to the phenol rather than later. The product, when solvent-free, is clear, dark-red, soft:- and tacky, and xylene-soluble.

DIEHENYLOLMETHANE Emcmpl'e 9 Use P-Qyclohexylphenol, 352 lbs.; heptaldehyde, 119.5. lbs. (molal ratio, 2 to 1.05); concentrated sulfuric acid, 4 lbs.;' xylene, 100 lbs. Proceed as in. Example 8 above. The product, when sol,- vent-free, is clear, soft, tacky, dark red and xylone-soluble.

DIPHENYLOLMETHANE Example 10 Use p--tertiary hexyl-phenol, 1.78 lbs; formaldehyde (37%) 43 lbs. (molal ratio, 1 to 0.53),; concentrated hydrochloric acid, 2 lbs; Nacconal NRSF (a, product of National Aniline Co.),, 0.8 lb-.; and xylene, 100 lbs. Proceed as in Example 3 above. The. product, when solvent-free, clear, reddish-amber, soft and tacky, and xylenesoluble. 1

DIPHENYLOLMETHANE Emampla 1.1

Use p-phenylphenol, 340 lbs; butyraldehyde, (5.6 lbs. (molal ratio, 2 to 1.05); concentrated sulfuric acid, 4 lbs.; and xylene, 100 lbs. Proceed as in Example 3, above. On evaporating the xy" lene solution of the product, some pphenylphenol sublimes, showing incompleteness of the reaction. The product, when solvent-free, is reddish-black, quite hard, opaque, and xylenedispersible.

DIPHENYLQLMETHAN E Example 12 Use petertiary amylphenol, 328,.l bs.; formaldehyde (37%)., 81.2 lbs. (molal ratio, 2 to 1) concentrated hydrochloric acid, 1.5 lbs..; and Nacconal NRSF (a product of National Aniline Co), 0.5 lb. Heat the mixture to 80 C. After the exothermic reaction subsides, reflux for 1 hour. Remove. the water of solution and of reaction by distillation, to C. The. product, when solvent-free, is. a light-yellow viscous. oil.

DIPHENYLOLMETHANE Example. 13

Use p-octad'ecyl'phenol, 87 lbs; formaldehyde Q37 10.5 lbs. (molal ratio, 2 to 1); concentrated hydrochloric acid, 1 1b.; Nacconal NRSE (a' product of National Aniline Co.), 0.2 lb.; and xylene, 5.0 lbs. Proceed as in Examples 1 and 3 .7 above, in that the procedure of Example 1 is followed except that the xylene is added to the phenol before the formaldehyde is added. The

product, when solvent-free, is clear, reddish, soft,

tacky, and xylene-soluble.

DIPHENYLOLMETHANE Example 14 Use p-nonylphenol, 220 lbs; formaldehyde .(3'7'%), 43 lbs. (molal ratio, 1. to 0.53); concentrated hydrochloric acid, 2 lbs. Nacconal NRSF (a product of National Aniline 00.), 0.8 lb; and xylene, 100 lbs. Proceed as in the preceding example. The product, when solvent-free, is clear, reddish, soft-to-fiuid, and xylene-soluble.

In general, preparation of the diphenylolmethane may be accomplished merely by reacting the phenol and the aldehyde in absence of added inert solvent. However, if the use to which the final product is to be put does not rule out the use of such solvents, they are often employed to advantage, as shown by the foregoing examples. For example, xylene or high-boiling aromatic petroleum solvent may be included in the reaction mass to reduce its viscosity. On completion of the reaction, it facilitates removal of the water of solution (if the aldehyde was used in aqueous solution) and the water of reaction. We prefer to employ such solvent at this point in the preparation of such of our reagents as are ultimately to be used as demulsificrs as above noted, because the finished demulsifying agent will probably be required to contain a viscosity-reducing solvent anyway, if it is to be used commercially.

Having prepared the parent diphenylolmethane by the foregoing or other procedures--details of such preparation being well known and also bein shown in the examples above, or the materials having been purchased, if obtainable-we next oxyalkylate that material.

Oxyalkylation of such 'diphenylolmethanes, as above stated, results in the interposition of an alkyleneoxy group or multiples thereof between the original phenolic hydroxyl oxygen atom and its companion hydrogen atom; and the conversion of such original phenolic hydroxyl groups into alcoholic hydroxyl groups. Because such oxyalkylation procedure introduces oxygen atoms into the molecule being treated, in the form of ether linkages, it generally confers increasing water-solubility on such molecule. Particularly, in such cases, it confers increasing water-solubility by small increments, so that substantially any desired level of water-solubility, water-dispersibility, or self-emulsifiability may be conferred simply by controlling the number of alkyleneoxy groups so introduced. For different purposes, it may be desired to have higher or lower levels of oxyalkylation.

For reagents which are effective as demulsifiers for crude oil emulsions of the water-in-oil type, we prefer to employ a relatively high level of oxyalkylation, and prefer to employ ethylene oxide to achieve it. In using ethylene oxide, we have found that in some cases surface-activity and self-emulsifiability begin to appear when."

there has been added about half as much ethylene oxide as there is diphenylolmethane present, in mols. For some purposes, where hydrophile qualities are desired, but with low water-solubility, such result might be achieved by using smaller proportions of ethylene oxide or by employing some higher alkylene oxide, e. g., butylene oxide, which has a smaller oxygen-to-carbon ratio and hence confers less water-solubility per molecule added than does ethylene oxide.

oxyalkylation is a, well known procedure. The alkylene oxide is added, either continuously or batchwise, in gaseous or liquid form, to the liquid or molten diphenylolmethane, at a temperature at which the alkylene oxide will be absorbed. While the reaction is an exothermic one, it is usually required to heat the parent diphenylolmethane at the beginning of the reaction, and sometimes throughout it, to temperatures generally lying between 50 and 250 0. Reaction is pref-' "erably effected in a closed vessel, capable of withmust be practiced, or the stirring rate must be reduced, to reduce effectiveness of contact and consequent rate of reaction.

Catalysts are preferably employed in this reaction; and alkaline catalysts are more desirable than acidic catalysts. Caustic soda, alkali carbonates, alkali alcoholates like sodium methylate,

alkali soaps, etc., may be so used. The amounts employed usually lie between 0.2 and 2%, by

weight, of the diphenylolmethane.

In all instances the proportion of alkylene oxide employed is sufiicient to produce self-emulsifiability of the diphenylolmethane. In the case of ethylene oxide, about 0.5 to 2 mols per mol of diphenylolmethane may be required to produce incipient water-dispersibility and surface-activity.

Addition of alkylene oxide may be continued to any level desired, for the units of alkylene oxide continue to interpose themselves between the oxygen atom and the hydrogen atom of the free hydroxyl groups present (the first such unit added to each original phenolic hydroxyl group transforming it into an alcoholic hydroxyl group).

If the oxyalkylated diphenylolmethane is to be used as an intermediate in the preparation .of a

fractional or total ester, the influence of the esterifying acid on the surface-activity of the resulting ester must be considered. For instance, if one employs an oxyalkylated diphenylolmethane l which is itself only marginally surface-active, and

esterifies it with a monocarboxylic acid having, for example, 18 carbon atoms, it is possible that the efiect of such esterifying acid will be such as to remove the resulting esterv from the class of reagents acceptable in our invention, because such ester may exhibit negligible surface-activity.

In another case, the intermediate oxyalkylated diphenylolmethane employed in such esterification may show undesirably high and almost true water-solubility; but the effect of the high molal esterifying acid would tend to reduce the watersolubility, and the resulting ester might show more desirable surface-activity for that purpose.

One method of varying the oxyalkylation level is to add a small proportion of alkylene oxide, substantially sufiicient to convert only one of the two phenolic hydroxyl groups to an alcoholic hydroxyl group; then to esterify this alcoholic group with the desired high molal acid; and then to revert to oxyalkylation to introduce sufiicient alkylene oxide to solubilize the fractional ester to the desired level.

Surface-activity of the reagents of our invention is determinable quantitatively by finding the surfaceor interfacial tension of dilute aqueous dispersions, e. g., by means of a DuNouy tensiometer or dropping pipette, etc. A value considerably lower than that of the solution water should be found in dilutions of 1% and less, if the dis- .solved substance is surface-active.

If it were truly dissolved in the water, the values would ap proximate that of water. Unless the reagent has been solubilized at least to the extent that a dilute of 'its' surfaceor interfacial tension. Theacceptabiilty of a reagent in our invention is determined by the fact that it has at least sumcient surface-activity to produce an aqueous dispersion of 0.5% to concentration which is which are at least of such minimum stability. In-

suificiently solubilized reagents are consequently excluded from the scope Of our invention.

As examples of methods for preparing oxyalkylated diphcnylolmethanes of the present class, We submit the fOllOWing:

.OXYALKYLATED DIPHENYLOLMETHANE Example 1 The xylene-free product of Example 12, Di-' phenylolmethane, above, (at least 85% pure),

274.8 lbs... is mixed with 87.7 lbs. of xylene, and

5.4 lbs. of sodium methylate. Ethylene oxide is added in 100-lb, lots. On addition of the first 100 Has, the temperature maximum was 140 C., the pressure maximum was 65 p. s. 1. gauge. In 0.5 hour, a llght-amber-colored oil was produced, which made a milky water dispersion that separated on standing (in presence of the xylene). Addition of a second 100-lb. lot of ethylene oxide, with maximum temperature of 160 C. and maximum pressure of 90 p. s. i., gave, in 3 hours, a non-viscous oil which showed a stable milky dis persion with water. Another 100-lb. lot of ethylone oxide was reacted with maximum tempera- 40 ture of 150 C. and maximum pressure of 160 p. s. i. In i hours, a non-viscous oily liquid, emulslfiable in water, was produced. Another 100-lb. lot of ethylene oxide, at 153 C. maximum temperature and 110 p. s. i. maximum pressure, after 3.5 hours, produced a material which, al though still making a cloudy dispersion in water, was obviously becoming more water-dispersible. A final 100-lb. lot of ethylene oxide further im-- proved the water-dispersibility of the material slightly.

OXYALKYLATED DIPHENYLOLMETHANE Example 2 The diphenylolmethanes of Examples 1 to 11,

13 and 14, Diphenylolmethane, preceding, are substituted in the oxalkylation procedure recited immediately above.

OXYALKYLATED DIPHENYLOLMETHANE Example 3 The diphenylolmethanes of Examples 1 to 14, Diphenylolmethane, above, are used in the oxyalkylation procedure of Example 1 immediately above, except that propylene oxide or butylene somewhat above 190 C, Completeness of the reaction may be followed in such cases by noting the amount of water of reaction which is distillable; or it may be followed by determining the reduction'in free carboxyl group. For fractional esters, of course, the proportion of esterifying acid must be limited to the molal proportion required to esterify only a part of the alcoholic hydroxyl groups present. It has already been stated that functional equivalents of the free high molal acids may be employed in this esterification reaction.

FRACTIONAL HIGH MOLAL ESTER OF OXY- ALKYLATED DIPHENYLOLMETHANE Example 1 One mol of the oxyalkylated diphenylolmethane produced in Oxyalkylated Diphenylolmethane, Examples 1 to 3 above (at least pure except for solvents) is reacted with an equi-molar proportion (282 parts) of oleic acid, in xylene solution. After refluxing 1 hour, the vessel containing the mixture is fitted with a side-arm trap and is heated to distill the approximately 18 parts of water produced in the esterification.

FRACTIONAL HIGH MOLAL ESTERiOF oxy- ALKYLATED DIPHENYLOLMETHANE Example 2 Repeat Example 1 immediately above, except use 298 parts of ricinoleic acid as the esterifying acid.

FRACTIONAL HIGH MOLAL ESTER OF OXY- ALKYLATED DIPHENYLOLMETHANE Example 3 Repeat Examples 1 and 2 immediately above, exceptuse 280 parts of linoleic acid or 278 parts of linolenic acid as the esterifying acid.

FRACTIONAL HIGH MOLAL ESTER OF OXY- ALKYLATED DIPHENYLOLMETHANE Example 4 FRACTIONAL HIGH MOLAL ESTER OF OXY- ALKYLATED DIPHENYLOLMETHANE Example 5 Repeat Examples 1 to 4 immediately above, except use approximately 280 parts of soy bean fatty acids as the esterifying' acid.

When one employs twice as many mols of high molal esterifying acid as of 'oxyalkylated diphenylolmethane (assuming non-hydroxylated alkylene oxides were used), in the above esterification procedure, total esters are formed. Such total esterification reactions are even easier to conduct than those employed to produce fractional esters, because the presence of excess esterifying acid is not important. It may be removed at the end of the reaction, or it may be allowed to remain in the mass, if its presence is not undesirable in the projected use of the total ester. Employment of the methyl or ethyl ester of the esterifying acid is quite practicable here. The free acids, their acyl chlorides, their anhydrides, etc., may be equally well employed as in the case of the preparation of the fractional esters above.

TOTAL HIGH MOLAL ESTER OF OXYALKYL- ATED DIPHENYLOLMEI'HANE Example 1 Repeat the procedure of Fractional High Molal Ester of Oxyalkylated Diphenylolmethane, Examples 1 to 5, above, except use twice as much of the fatty acid in each case. (Note that four or more times as much high molal acid as in the preceding examples would be required to produce total esters from oxyalkylated diphenylolmethanes prepared from glycide or methylglycide.)

TOTAL HIGH MOLAL ESTER OF OXYALKYL- ATED DIPHENYLOLME'I'HANE Example 2 Repeat Example 1 immediately above, except use an equivalent amount of the respective acyl chloride instead of the free fatty acid in each case. Note that hydrogen chloride, not water, will be the other product of the esterification reaction here.

So long as one of the alcoholic hydroxyl groups of the oxyalkylated diphenylolmethane has been esterified with a high molal monocarboxylic acid, as above illustrated, the remaining such hydroxyl group or groups may be esterified with a low atoms or less, to produce a mixed ester. The following examples embody this phase of our reagents.

MIXED ESTER OF OXYALKYLATED DIPHENYLOLMETI-IANE Example 1 The fractional esters produced in Fractional High Molal Ester of Oxyalkylated Diphenylolmethane, Examples 1 to 5 above, are heated with proportions of either acetic acid, hydroxyacetic acid, lactic acid, or butyric acid, sufficient to esterify the remaining free alcoholic hydroxyl groups present in such fractional esters. An equivalent amount of water of esterification is distilled off, after suitable refluxing; and mixed esters of said oxyalkylated diphenylolmethanes are the resulting roduct.

If a total ester containing the residue of a hydroxylated monocarboxylic acid is desired, it is, preferable to produce the fractional ester of any non-hydroxylated acid employed; and to use the latter in the second esterification step. This avoids any possibility of reaction between the hydroxyl group of the hydroxylated acid and the carboxyl group of the other acid, in preference to reaction between the free alcoholic hydroxyl group of the oxyalkylated diphenylomethane and the non-hydroxylated acids carboxyl group. For example, if ricinoleic acid and a low molal nonhydroxylated acid are to be esterified, the ricinoleic acid is preferably reacted last.

In the foregoing discussion, no consideration has been given the thought that symmetrical and unsymmetrical forms of oxyalkylated diphenylolmethanes may be prepared. For example, minimum oxyalkylation may be conducted, so as to introduce a total of two mols of alkylene oxide, which convert the two phenolic hydroxyl groups to alcoholic hydroxyl groups. Then, one of the alcoholic hydroxyl groups may be blocked by reacting the partially oxyalkylated productwith an acid, e. g., a high molal monocarboxylic acid, to produce a fractional ester. Such fractional ester may then be oxyalkylated further, all of the additional alkylene oxide being added at the 'molal monocarboxylic acid, containing 7 carbon If desired, this Same procedure may be applied,

but more alkylene oxide introduced in the first oxyalkylation step. In such instance, both alcoholic hydroxyl groups would receive a number of alkylene oxide residues. Esterification at one of such two positions would then prevent any further addition of alkylene oxide there; and any further oxyalkylation must consequently take place at the other position. This latter position would then have more alkylene oxide residues than the first and esterified position; and the product would likewise be unsymmetrical.

Where all oxyalkylation takes place before any esterification, in a single preliminary operation, distribution ofalkylene oxide residues between the alcoholic hydroxyl positions will be uniform if the two phenolic nuclei are identical; and symmetrical oxyalkylated esters will result on subsequent esterification.

Materials of the kind herein disclosed are useful in many arts. They may be used as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid-washing of fruit and in the acid-washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like; as a constituent of soldering flux preperations; as a flotation agent in the flotation separation of various minerals; for flocculating and coagulating negatively-charged particles from various aqueous suspensions such as sewage, coal-washing waste water, various trade wastes, and the like; as germicides and insecticides; as emulsifiers for cos-. metics, spray oils, water-repellent textile finishes, etc. The aforementioned uses are by no means exhaustive as to industrial uses. The most important use of our new composition of matter is as a demulsifier for dehydrating water-in-oil emulsions, and more specifically emulsions of water or brine in crude petroleum.

The chemical reagents herein described are also particularly desirable for use as break inducers in the doctor treating procedure for sweetening gasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton.)

Chemical compounds of the kind herein described are also of value as surface tension depressants in the acidization of calcareous oilbearing strata by means of strong mineral acid, like hydrochloric acid. As to this use, see U. S. Patent No. 2,233,383, dated February 25, 1941, to DeGroote and Keiser. similarly, some members are effective as surface tension depressants or wetting agents in the working of depleted oilbearing strata by flooding in secondary recovery operations. As to this last-named use, see U. S. Patent No. 2,226,119, dated December 24, 1940, to DeGroote and Keiser,

We have prepared a number of representative oxyalkylated diphenylolmethanes and esters thereof, as described herein. We have tested such representative oxyalkylated diphenylolmethane products and their esters as herein described and have found them to be efiective demulsifiers for oil-field emulsions of the water-in-oil type. We have additionally determined that such oxyalkylated products and their esters are valuable for purposes where surface-active agents are conventionally employed. We have also determined that 19 the oxyalkylated products and their estersherein described can-be used as intermediates for the manufacture of more complicated derivatives.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such,.or after dilution with any suitable solvent. Suitable solvents include water; various petroleum hydrocarbons, particularly aromatic or cyclic fractions; coal tar hydrocarbons like benzene, toluene, Xylene, tar acid oil, cresol, anthracene oil;- alcohols, particularly aliphatic alcohol like methyl, ethyl, isopropyl, butyl, hexyl, octyl, etc.; pine oil; carbon tetrachloride; etc. Our reagents may be admixed with one or more of such conventional solvents. Furthermore, our reagents may be used alone or admixed with other suitable chemical demulsifying' agents.

Demulsifiers are sometimes used in Water-soluble form, sometimes in oil-soluble form. Sometimes they are both oiland Water-soluble; and sometimes they exhibit little solubility in either oilor water. However, when used at customary ratios, which may vary from 1 to 5,000 to about 1 to 50,000 or less, demulsi-fier-to-emulsion, any apparent insolubility in bulk is not significant. Within the concentrations employed, said reagents undoubtedly have appreciable solubility in-both water and oil. This is true also. as to our reagents.

The superiority of the reagent or demulsifier of our process is based upon its ability to resolve certain emulsions more efiectively and at somewhat lowe cost than is possible with other available. demulsifiers or mixtures thereof. We be.-. lieve the demulsifying agents of this invention may find comparatively limited use so. far as the. majority of oil field emulsions are concerned; but we :have found that. such demulsifier has com-. mercial value in that it will break or resolve economically oil-field emulsions in a number of cases where the demulsifiers hitherto available are ineffective or less effective and less economical.

In practicing our process for resolving petro.-. leum emulsions. of the water-.in-oil type, a demulsifying agent .of the kind described herein is brought into contact with or caused to act upon the emulsion to be resolved, in any of the various apparatus now used in connection with such resolution processes involving chemical demulsifyin agents. t maybe used alone or in. combination with other demulsifyine procedures such aselectrical dehydration.

Our reagent may be employedv in what is .com-.

' monly known as down-the-hole procedure, in

which the reagent is brought into contact with the. Well fluids before they reach the surface. of the. ground. Such procedure or a modification thereof is especially useful in acidizing oil-.bear.-. i-ng calcareous strata to improve their roduc= tivity, wherein the reagent may be dissolved or dispersed or suspended in the acid used.

In some cases, our reagent may be. used without dilution. However, it may be. admixed with any suitable solvent. For instance, a preferred mixture contains 50% of our concentrated reagent, 40% xylene, and isopropyl alcohol. The se-. lection of solvent will depend on solubility characteristics of the reagent, on the solidifying point which may be tolerated, etc. Frequently it will, depend largely on solvent cost.

As an example of admixtures. of our reagent. with other demulsifiers, the following may be recited: Use a reagent of the. present invention, 211%.; a cyclohexylamine salt of a. propylated ap t al e sulf nie acid. 2.0%; an am onium. salt of a propylated naphthalene sulfonic acid, 20%; a sodium salt of an oil-soluble petroleum sulfonic (mahogany) acid, 10%; a high-boiling aromatic petroleum solvent, and isopropyl alcohol, 5%. All percentages are by Weight.

The reagents of our invention are used as demulsifiers for petroleum emulsions in methods and procedures which have long been conventional and routine in the art. Thesemethods are used in thousands of producing wells daily in re.- covering large volumes of crudeoil from emulsia fled form. r

One broad type of procedure is to accumulate a volume of emulsified-oil and then to resolve it in a tank by a batch treatment operation. In this procedure, the emulsion is admixed with the demulsifier, for example by agitating the tank of emulsion and slowly dripping in the demulsifier.

In some cases, mixing is achieved by heating the contents of the tank while dripping in the reagent, depending on convection currents to produce satisfactory admixture. In another modification of this broad type of procedure, a circulating pump is used to transfer emulsion from one tank to another or to withdraw emulsion from the bottom of a tank and return it to the top thereof, the demulsifier being added, for example, into the stream at the suction side ofsaid pump.

I Heat'may be employed; but is sometimes unnec essar-y.

A second type of treating procedure involves introducing demulsifier into the well fluids at the well-head orat some convenientpoint in the line between the well-head and the final storage tank. An adjustable proportioningmechanism or pump is usually employed to meter reagent into such fluids. Ordinarily, the flow of fluids through the line furnishes sufficient agitation to ad'miX emul sion and demulsifier satisfactorily; but mechanie cal mixing devices may be incorporated into the, flow system. Various mechanical devices, for- Withdrawing unemulsified water, separatingentrained water, or accomplishing quiescent set-.

' tling of the chemicalized emulsion. are some-.

times employed. Heating devices may likewise be employed and incorporated in any of the treating procedures described herein, if desirable or necessary to achieve satisfactory oroptimum results.

A third broad demulsifier application procede ure is to introduce the reagent continuouslyor intermittently into the annulus of the well and permit it to come to the surface with the well fiuids, as above. stated; and then to flow such chemicalized fluids through any desirable surface equipment as the other procedures recited herein.

It is apparent from the. above description that, the process consists broadly in introducing a rel. atively small proportion of reagent i nto:a rela tively large proportion of emulsion, admixing the chemical and emulsion either through natural flow or with special apparatus, with or Without, he a l ation 0 684 and hen. all win th mixture to stand quiescent until the emulsified W ter pa a and; se es; f heg ss--.

In. a pica n tallation. a-con ainer w a 5.- to -ea1lonsupp y of'r a ent. (in e h r dilut d r undiluted o m) s. plac d a the wel' head. a d connected to a proper oninspump capable of injecting from 1 pint to'several. gallons of reagent a day into the fluids leaving the well. at: a rate of several drops. a minute. The reagent is. so introduced into. the. well fluids; and. the

21 chemicalized mixture is flowed through a gas separator and then to a tank capable of holding the amount of fluid produced in from 4 to 24 hours. This settling tank has a vertical conduit into which the well fiuids are discharged and by means of which they are conducted to the bottom of the tank before discharge into it. In this manner, the tank contents are not disturbed by the flow of incoming fluids. This settling tank may be fitted with heating coils so that it may be heated to from 90 to as much as 200 E, if desired, if heat is required. It may also be fitted with an automatic level control by mean of which the water layer in it is maintained at any desired level. The oil which leaves this settling tank through an overflow pipe is either substantially clean and dry or else is in the form of an unstable emulsion from which the undesirable water content separates after passage to a second tank and standing there. When the oil is satisfactorily dehydrated, it is passed to a storage or shipping tank, from which it is sold.

In starting such a demulsification operation, the chemical feed is usually excessive at first, as to ultimate cost, so as to insure recover of clean, dry oil. The feed rate is progressively reduced until the amount being injected is just sufiicient to maintain the oil leaving the system at a satisfactory level of water content. For instance, the ratio of reagent to oil may be 1 to 2,500 or 1 to 5,000 at the start of the operation; but within a few days it may be found that a ratio of 1 to 10,000 or 1 to 20,000, or even less, is ample to accomplish the purpose. While the examples show a number of representative usable phenols, it may be well to describe our preferred trifunctional phenolic reactants here. These are prepared from the phenolic compositions present in or derived from the oils extracted from the anacardium genus of the anacardiaceae family. Cashew nutshell liquid is described as consisting of about 90% anacardic acid, 022113203, and cardol, C32H52O4, with very small fractional percentages of other materials. Anacardic acid is generally accepted to be:

nHrr Pyrolytic distillation causes conversion into phenols. Our reagents may be obtained from cashew nutshell liquid, anacardol (3-pentadecadienylphenol), cardanol (dihydroanacardol or 3- pentadecenylphenol) and hydrogenated cardanol (dihydrocardonal or tetrahydroanacardol or 3- pentadecylphenol). Commercially, these products appear on the market in one of three forms:

cardanol, treated cashew nutshell liquid, and hydrogenated cardanol. ,,As an example of a diphenylolmethane prepared from one such tri-functional phenol, and suitable for subsequent oxyalkylation, the following directions may be given: Use cardanol, 576 grams; formaldehyde (37%), 81 grams (molal ratio, 2 to l); concentrated hydrochloric acid, 4 grams; Nacconal NRSF (a product of National Aniline Co.) 1.5 grams. Proceed as in Example 1 Diphenylolmethane, above, except that the xylene is added just before water is distilled. The product, when solvent-free, is dark red, soft or semi-fluid, and xylene-soluble.

Attention is directed to the fact that the present application is one of a series, Serial Nos.

22 751,601, 751,602, 751,603, and 751,604, all filed of even date, and all relating to kindred subjectmatter.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a reagent comprising a surface-active oxyalkylated derivative of a diphenylolmethane having the formula wherein one occurrence of R2 represents hydrogen and the other occurrence represents a member of the class consisting of hydrogen and organic radicals containing 7 carbon atoms or less; R4 is a member of the class consisting of alkylene radicals and hydroxyalkylene radicals and contains 4 carbon atoms or less; R6 is a monocyclic phenolic nucleus; R5 is a member of the class consisting of (a) hydrocarbon radicals containing from 1 to 24 carbon atoms and located in the para position of the phenolic nucleus Re, and (b) hydrocarbon radicals containing from 9 to 24 carbon atoms and located in the 3,5 position of the phenolic nucleus Re; R! is a member of the class consisting of hydrogen, acyl radicals of monocarboxylic acids having from 8to 32 carbon atoms, and acyl radicals of monocarboxylic acids having less than 8 carbon atoms, with the proviso that if either occurrence of R1 represents an acyl radical, at least one such occurrence must represent the acyl radical of a monocarboxylic acid having from 8 to 32 carbon atoms; that n is a number between 1 and 60; and with the final proviso that said derivative, in absence of waterinsoluble solvents, is surface-active to the extent that it is capable of forming at least a semistable aqueous dispersion in 0.5% to 5% concentration, said surface-activity being due to oxyalkylation in the phenolic hydroxyl Position.

2. The process of claim 1 wherein R5 is a hydrocarbon radical containing from 1 to 24 carbon atoms and located in the para position of the phenolic nucleus Re.

3. The process of claim 1, wherein R5 is a hydrocarbon radical containing from 1 to 24 carbon atoms and located in the para position of the phenolic nucleus Ra; one occurrence of R2 represents hydrogen; and the other occurrence of R2 represents an aliphatic radical.

4. The process of claim 1, wherein R5 is a hydrocarbon radical containing from 1 to 24 carbon atoms and located in para position of the phenolic nucleus Re; and both occurrences of R2 represent hydrogen.

5. The process of claim 1, wherein R5 is a hydrocarbon radical containing from 1 to 24 carbon atoms and located in the para position of the phenolic nucleus Rs; both occurrences of R2 represent hydrogen; and R4 is the ethylene radical C2H4.

6. The process of claim 1, wherein R5 is a hydrocarbon radical containing from 1 to 24 carbon atoms and located in the para position of the phenolic nucleus Rs; both occurrences of R2 represent hydrogen; R4 is the ethylene radical C2H4; and both occurrences of n represent the same number.

7. The process of claim 1, wherein R5 is a hydrocarbon radical containing at least 6 carbon atoms and located in the para position of the atlases 23; phenolic nucleus Rs; both occurrences of R represent. hydrogen; R4 is the 'e hyl nera icm C234; and both occurrences of n represent the; same number.

8;. The process of claim 1, wherein one occurrence of R7 represents hydrogen and the other occurrences- 37 repr sents t a yl rad l of a mon carboxylic. acid. containing from :8 to 32. carbon atoms. 7 H

29.. The process of claim ,v w e e n Raise hydrocarbonradicai containing from .1' to 2.4. carbon atoms and located in the para position of the phenolic nucleus Re; and wherein one occurrence of R7 represents hydrogen-and the other occurrence of R7 represents the acyl radical of a monocarboxylic acid containing from 8 to. 32 carbon atoms.

10. The process of claim 1, wherein. R is-a hydrocarbon radical containing from 1 11124 carbon atoms andlocated in the paraposition of the phe nolic nucleus Be; one occurrence of R2 represents hydrogen; the other occurrence of R2 represents an aliphatic radical; one occurrence cf R; representshydrogen; and the other occurrenceof R represents the acyl, radical of a monocarbcxylic acid containing from 8 to 32 carbon atoms.

11. Theprocess of claim'l, whereinRs. is a. hydrocarbonradical containing from 1 to. 24 carbon atoms, and located in, the para position of the phenolic nucleus Rs; both occurrcncesof R2 represent hydrogen; one occurrence of R7 represents hydrogen; and the other occurrence of R represents the acylradical of a monocarboxylic acid containing fromB .to. 32 carbon atoms.

12. The process of claim 1, wherein R isa hydlfocarbon radical containing from v1 to 2.4 carbon atoms and located in the para position of the phenolic nucleus. R6; both occurrences of rep: resent hydrogen; R4 is the ethylene radical CzHg; one occurrence of R7 represents hydrogen; and the other occurrence of R7 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbonatoms.

1?. The process of claim 1 wherein Raise. hydrocarbon radical containing from 1 to .4; carbon atoms and located in the-para position of the phenolic. nucleus Re; both occurrences of R represent hydrogen; R4 is the ethylene radical (321 h; one occurrence of R7 represents, hydrogen; the other occurrence of R7 represents the acyl radical of a monocarboxylic acid containing from 8 t 32 carbon atoms; and both occurrences of n, represent. th same number.

14. The process of claim 1,v wherein R5 isa'hy- ,drocarbon radical containing at least 6 carbon atoms and located in the para position of the phenolic nucleus Rs;'both occurrences of R rep resent hydrogen; R4 is the ethylene radical Cal-I4 one occurrence of R7 represents hydrogen; the

other occurrence of R7 represents the acyl radical of a monocarboxylic acid containing frcm s to .32 carbon atoms; and both occurrences ofn represent the same number. 15. The process. of claim 1, wherein one occurrence of R7 represents the acyl radical of -a monocarboxylic acid containing from .8 to 32 carbon atoms, and the other occurrence of R7 represents the acyl radical of a monocarboxylic acid containing from 1 to32. carbon atoms.

16. The process of claim 1, wherein R5 isa hydrocarbon radical containing from 1 to 24 carbon atoms and located in the para position of the phenolic nucleus Re; wherein one occurrence of R7 represents the acyl radical of a monocarboxylic 24: acid containing from 8 to 32. carbon atomsyand the other occurrence of R7, represents the acyl radical of a monocarboxylic acid containing from 112932 carbon atoms.

17. The process of claim 1, wherein Rsis .a hydrocarbon. radical containing from 1 to 24 carbon atoms and located in the para position of the, phenolic nucleus Be; one occurrence of R2 representshydrogen; the other occurrence of R2 rep.- resents an aliphatic radical; one occurrence of R7 represents the acyl radical of a monocarboxylic: acid containing from 8. to 32 carbon atoms; and the other occurrence of R7 represents the .acyl radical of 'a monocarboxylic acid containing from 1 to 3-2 carbon atoms,

18. The process of claim 1, whereinRs isq'a hydrocarbon radical-containing-from 1 to 24 carbon atoms and located in the para position of thephenolic nucleus Rs; both occurrences of R2, represent hydrogen; one occurrence of R7 represents the acyl radical of a monocarboxylic, acid containing from 8 to 32 carbon atoms; and the other occurrence of :R7 represents the acyl radical of a monocarboxylic acid containing from -1 to 32-.carbon atoms.

19. The process of claim 1, wherein R5 is a laydrocarbonradical containing froml to 24 carbon atoms and located in the para position of the phenolic nucleus R6; both occurrences of- R2 represent hydrogen; R4 is'the ethylene radical Cal-L one occurrence of R7 represents the acyl radical of a monocarboxylic acid containing from 8 to 32 carbon atoms; and the other occurrence of R7 represents the acyl radical of a monocarboxylic acid containing from 1 to 32 carbon atoms.

20-. The-process of claim 3., wherein R5 is a h-ydrocarbon radical containing from Ito 24-carb0n atoms and located in the para position of the phenolic nucleus R s; both occurrences of R2 represent hydrogen;v R4 is the ethylene radical of C2H4; one occurrence of R7 represents the acyl radical of a monocarboxylic acid containing from 8 to 3-2 carbon atoms; the other occurrence of R7 represents the acyl radical of a monocarboxy-lic acid containing from 1 to 32 carbon atomsyand both occurrences of n represent the same number.

21. The process of claim 1,.wherein R5 is a hydrocarbon radical containing at least 6 carbon atoms and located in the para position of the phenolic 7 nucleus Rs; both occurrences of R2 represent hydrogen; R4 is the ethylene radical C2H4 one occurrence of R7 represents the acyl radical of a monocarboXyl-ic acid containing from 8 to 32 carbon atoms; theother occurrence of R7 represents the acylradical of a monocarboxylic acid containing from I to 32 carbon atoms; and both 00'- currences of n represent the same number.

MELVIN DE GROO-IE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file of this patent: 7

UNITED STATES PATENTS,

De Groote et a1 Oct- 2, 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A REAGENT COMPRISING A SURFACE-ACTIVE OXYALKYLATED DERIVATIVE OF A DIPHENYLOLMETHANE HAVING THE FORMULA 